Fundamentals of Electrochemistry

Fundamentals of Electrochemistry
Introduction From: http://bionmr.unl.edu/course.php?id=chem221

1.) Electrical Measurements of Chemical Processes

Redox Reaction involves transfer of electrons from one species to another.
- Chemicals are separated

Can monitor redox reaction when electrons flow through an electric current
- Electric current is proportional to rate of reaction
- Cell voltage is proportional to free-energy change

Batteries produce a direct current by converting chemical energy to electrical
energy.
- Common applications run the gamut from cars to ipods to laptops
Basic Concepts

1.) A Redox titration is an analytical technique based on the transfer of
electrons between analyte and titrant

Reduction-oxidation reaction

A substance is reduced when it gains electrons from another substance
- gain of e
-
net decrease in charge of species
- Oxidizing agent (oxidant)

A substance is oxidized when it loses electrons to another substance
- loss of e
-
net increase in charge of species
- Reducing agent (reductant)

(Reduction)
(Oxidation)
Oxidizing
Agent
Reducing
Agent
Basic Concepts

2.) The first two reactions are known as 1/2 cell reactions
Include electrons in their equation
3.) The net reaction is known as the total cell reaction
No free electrons in its equation

4.) In order for a redox reaction to occur, both reduction of one compound
and oxidation of another must take place simultaneously
Total number of electrons is constant
cell reactions:
Net Reaction:
Basic Concepts

5.) Electric Charge (q)
Measured in coulombs (C)
Charge of a single electron is 1.602x10
-19
C
Faraday constant (F) 9.649x10
4
C is the charge of a mole of
electrons

6.) Electric current
Quantity of charge flowing each second
through a circuit
- Ampere: unit of current (C/sec)
F n q - =
Relation between
charge and moles:
Coulombs moles
e mol
Coulombs
Basic Concepts

7.) Electric Potential (E)
Measured in volts (V)
Work (energy) needed when moving an electric
charge from one point to another
- Measure of force pushing on electrons
q E work G - = = A
Relation between
free energy, work
and voltage:
Joules
Volts Coulombs
Higher potential
difference
Higher potential difference requires
more work to lift water (electrons) to
higher trough
Basic Concepts

7.) Electric Potential (E)
Combining definition of electrical charge and potential
q E work G - = = A F n q - =
nFE G = A
Relation between free energy
difference and electric potential
difference:
Describes the voltage that can be generated by a chemical reaction
Basic Concepts

8.) Ohms Law
Current (I ) is directly proportional to the potential difference (voltage)
across a circuit and inversely proportional to the resistance (R)
- Ohms (O) - units of resistance

9.) Power (P)
Work done per unit time
- Units: joules per second J/sec or watts (W)
R
E
I =
I E
s
q
E P - = - =
Galvanic Cells

1.) Galvanic or Voltaic cell
Spontaneous chemical reaction to generate electricity
- One reagent oxidized the other reduced
- two reagents cannot be in contact
Electrons flow from reducing agent to oxidizing agent
- Flow through external circuit to go from one reagent to the other
Net Reaction:
Reduction:
Oxidation:
AgCl(s) is reduced to Ag(s)
Ag deposited on electrode and Cl
-
goes into solution
Electrons travel from Cd
electrode to Ag electrode
Cd(s) is oxidized to Cd
2+
Cd
2+
goes into solution
Galvanic Cells

1.) Galvanic or Voltaic cell
Example: Calculate the voltage for the following chemical reaction
AG = -150kJ/mol of Cd
V .
C
J
.
mol
C
. ) mol (
J
E
nF
G
E nFE G
777 0 777 0
10 649 9 2
10 150
4
3
+ = + =
|
.
|
\
|

=
= =
A
A
Solution:
n number of moles of electrons
Galvanic Cells

2.) Cell Potentials vs. AG
Reaction is spontaneous if it does not require external energy
Galvanic Cells

2.) Cell Potentials vs. AG
Reaction is spontaneous if it does not require external energy
Potential of overall cell = measure of the tendency of this reaction to proceed to
equilibrium
Larger the potential, the further the reaction is from equilibrium
and the greater the driving force that exists

Similar in concept to balls
sitting at different heights
along a hill
Galvanic Cells

3.) Electrodes
Cathode: electrode
where reduction takes
place
Anode: electrode
where oxidation takes
place
Galvanic Cells

4.) Salt Bridge
Connects & separates two half-cell reactions
Prevents charge build-up and allows counter-ion migration
Two half-cell reactions
Salt Bridge
Contains electrolytes not
involved in redox reaction.

K
+
(and Cd
2+
) moves to cathode with
e
-
through salt bridge (counter
balances charge build-up

NO
3
-
moves to anode (counter
balances +charge build-up)

Completes circuit

Zn|ZnSO
4
(a
ZN
2+ = 0.0100)||CuSO
4
(a
Cu
2+ = 0.0100)|Cu
anode
Phase boundary
Electrode/solution interface
Solution in contact with
anode & its concentration
Solution in contact with
cathode & its concentration
2 liquid junctions
due to salt bridge
cathode
Galvanic Cells

5.) Short-Hand Notation
Representation of Cells: by convention start with anode on left
Ag
+
+ e
-
Ag(s) E
o
= +0.799V
Standard Hydrogen Electrode (S.H.E)
Hydrogen gas is bubbled over a Pt electrode
Pt(s)|H
2
(g)(a
H
2
= 1)|H
+
(aq)(a
H
+ = 1)||
Standard Potentials

1.) Predict voltage observed when two half-cells are connected
Standard reduction potential (E
o
) the measured potential of a half-cell
reduction reaction relative to a standard oxidation reaction
- Potential arbitrary set to 0 for standard electrode
- Potential of cell = Potential of reaction

Potentials measured at standard conditions
- All concentrations (or activities) = 1M
- 25
o
C, 1 atm pressure
Standard Potentials

1.) Predict voltage observed when two half-cells are connected
As E
o
increases, the more
favorable the reaction and the
more easily the compound is
reduced (better oxidizing
agent).

Reactions always written as
reduction
Appendix H contains a more extensive list
Standard Potentials

2.) When combining two cell reaction together to get a complete net
reaction, the total cell potential (E
cell
) is given by:
+
= E E E
cell
Where: E
+
= the reduction potential for the cell reaction at the positive electrode
E
+
= electrode where reduction occurs (cathode)
E
-
= the reduction potential for the cell reaction at the negative electrode
E
-
= electrode where oxidation occurs (anode)
Electrons always flow towards
more positive potential
Place values on number line to
determine the potential difference
Standard Potentials

3.) Example: Calculate E
o
, and AG
o
for the following reaction:
Nernst Equation

1.) Reduction Potential under Non-standard Conditions
E determined using Nernst Equation
Concentrations not-equal to 1M
aA + ne
-
bB E
o

For the given reaction:
The cell reduction potential is given by:
a
b
o
a
A
b
B o
] A [
] B [
log
n
V
E E
A
A
ln
nF
RT
E E
0.05916
=
=
Where: E = actual cell reduction potential
E
o
= standard cell reduction potential
n = number of electrons in reaction
T = temperature (K)
R = ideal gas law constant (8.314J/(K-mol)
F = Faradays constant (9.649x10
4
C/mol)
A = activity of A or B
at 25
o
C
Nernst Equation

2.) Example:
Calculate the cell voltage if the concentration of NaF and KCl were each
0.10 M in the following cell:
Pb(s) | PbF
2
(s) | F
-
(aq) || Cl
-
(aq) | AgCl(s) | Ag(s)
E
o
and the Equilibrium Constant

1.) A Galvanic Cell Produces Electricity because the Cell Reaction is
NOT at Equilibrium
Concentration in two cells change with current
Concentration will continue to change until Equilibrium is reached
- E = 0V at equilibrium
- Battery is dead
|
|
.
|
\
|
= =
+ +
d
b
o
a
c
o
cell
] D [
] B [
log
n
.
E
] A [
] C [
log
n
.
E E E E
05916 0 05916 0
aA + ne
-
cC E
+
o
dD + ne
-
bB E
-
o
Consider the following cell reactions:
Cell potential in terms of Nernst Equation is:
b a
d c
o o
cell
] B [ ] A [
] D [ ] C [
log
n
.
) E E ( E
05916 0
=
+
Simplify:
b a
d c
o
cell
] B [ ] A [
] D [ ] C [
log
n
.
E E
05916 0
=
E
o

1.) A Galvanic Cell Produces Electricity because the Cell Reaction is
NOT at Equilibrium
Since E
o
=E
+
o
- E
-
o
:
At equilibrium E
cell
=0:
K log
n
.
E
o
05916 0
=
Definition of
equilibrium constant
05916 0
10
.
nE
o
K =
at 25
o
C
at 25
o
C
E
o

2.) Example:
Calculate the equilibrium constant (K) for the following reaction:
Cells as Chemical Probes

1.) Two Types of Equilibrium in Galvanic Cells
Equilibrium between the two half-cells
Equilibrium within each half-cell
If a Galvanic Cell has a nonzero voltage then
the net cell reaction is not at equilibrium
For a potential to exist, electrons
must flow from one cell to the
other which requires the reaction
to proceed not at equilibrium.
Conversely, a chemical reaction within a
cell will reach and remain at equilibrium.
Ni(s)|NiSO
4
(0.0025M)||KIO
3
(0.10 M)|Cu(IO
3
)
2
(s)|Cu(s)
Cells as Chemical Probes

2.) Example:
If the voltage for the following cell is 0.512V, find K
sp
for Cu(IO
3
)
2
:
Biochemists Use E
o

1.) Redox Potentials Containing Acids or Bases are pH Dependent
Standard potential all concentrations = 1 M
pH=0 for [H
+
] = 1M

2.) pH Inside of a Plant or Animal Cell is ~ 7
Standard potentials at pH =0 not appropriate for biological systems
- Reduction or oxidation strength may be reversed at pH 0 compared to pH 7
Metabolic Pathways
Biochemists Use E
o

3.) Formal Potential
Reduction potential that applies
under a specified set of
conditions

Formal potential at pH 7 is E
o

b a
d c
o
cell
] B [ ] A [
] D [ ] C [
log
n
.
E E
05916 0
=
Need to express concentrations as
function of K
a
and [H
+
].
Cannot use formal concentrations!
E
o
(V)

Fundamentals of Electrochemistry

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Introduction From: http://bionmr.unl.edu/course.php?id=chem221

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